Highly wear-resistant zinc base alloy and method of making same



United States Patent I Motors Corporation, Detroit, Mich., a. corporation of Delaware.

No Drawing. Application July 5, 19 55 1 Serial N0.-520,'148 v This invention relates to an improved zinc base alloy and a. process for producing such an alloy. More particularly, the invention pertainsto an alloy of this type which is characterized by outstanding wear resistance properties due to the presence of hard particles of an iron-zirconium-aluminum alloy.

Zinc base alloys commercially used today for drawing dies and similar purposes usually possess inadequate wear properties for many requirements. It is therefore a principal object of the present invention to overcome this deficiency by providing a zinc base alloy characterized by greatly increased wear properties, high resistance to fracture, good 'castability -and homogenetity. Itis a further objectof this-invention to provide a drawing die formed of an inexpensive zinc base alloy which possesses high wear resistance, a low melting point and uniform shrinkage. 1

These and other objects and advantages are attained in accordance'with the present invention with a zinc base alloy containing a small amount of dispersed particles of iron-Zirconium-alurninum alloy. The iron-zirconiumaluminu'm particlescontain hard intermetallic compounds or phases of aluminum-zirconium which are primarily responsible for the. outstanding wear resistance of the In particular, we havefoiind that a zinc base alloy which contains smalllarnoiints of (copper. and additional aluminum, as well as the aforementioned hard particles, is especially suitable for use as a drawing die. A small amount of'magnesium also may beadvantageously included in the alloy. In this type of zinc base alloy the aluminum and copper are added to increase the tensile strength and hardness and to reduce the solidification temperature of the alloy. -"Magnesium is preferably included in the alloy to overcome the corrosive influence of any impurities which maybe lpr esent in the alloy. It thereforepromotes dimension'al stability and prevents a decrease in the'strength of the 'a1l0yj,oi1.a'ging'. The resultant material is a long-wearing, generally homogeneous alloy having goodcastability properties.'-

As disclosed infco-pehdin'g application Serial'No. .178,-

3.45, filed AiigtistS, 1950, in the-name of James C Holzwarth, now PatentNo. 2,720,459, patented'Oc'tober 11, 1955, the wear i'e's'is't anceof a zinc base' alloy may be improved'by the'inclu'sion of dispersed, hard particles of nickel-titainium'iiri the alloy. However, ironzirconiumaluminum alloysdo not contain any relatively critical nickel and hence are preferred in the event of a nickel 2,912,324 I Patented Nov. 10, 1959 out the zinc base alloy. As hereinafter more fully'exshortage because of a national emergency or for other reasons. aluminum alloy is appr'e'ciably less expensive than typical nickel-titanium.alloys. l I I In accordance with the invention'therefore, the afore mentioned beneficial properties are obtained to a particularly high degree in a zinc base alloy containing aluminum, copper and'magnesium by the inclusionthere Furthermore, the average iron-zirconium in' of iron-zirconium-aluminum in the form of small particles which are generally uniformly dispersed through;

plained, these particles may be advantageously introduced into the zinc-rich melt in the form of a copper base intermediate alloy. I

The low melting point of the zinc base alloy eliminates the need for elaborate equipment in the alloying procedure, only a comparatively simple gasor oil-fired melting kettle being required. The uniform shrinkagecharacteristic' of this alloy permits the exact size of castings to be predetermined with precision, eliminating the necessity for extensive use of profiling machines.

castings of this alloy can be produced comparatively quickly, making them available for production use within a relatively short time. i

Thehigh wear resistancepof the final zinc base alloy is due to the presence offthe dispersed, hard particles, of iron-zirconium-aluminum': alloy. Hard compounds. or phases are known to occurvin the binary system of zirconium-aluminum, but these'hard materials alone are generally unsuitable for inclusion in a cast zinc base alloy since their densities are lower than the density of the zinc-rich melt to which they are added. Particles of zirconium-aluminum therefore tend to float to the top of Y molten zinc base alloys and are of little value in applications where substantial homogeneity of the casting is. required. Furthermore, certain oil-these phases will .decompose or dissolvein molten zinc andlose their identity. However, we haveafound that these hard zircon' i1 1mv aluminum compounds can be combined with iron and-,.

with proper selection of 'compositions and alloying methods, the resultant iron-zirconium -aluminum alloy. can be made to remain iir'suspension in the moltenzinc base alloy as discrete hard particles which provide the final cast alloy with greatly increased-wear resistance; These hard particles do not readily float or settle out of the zinc-rich melt since they have a specific gravity which closely approximates that of the zinc-rich melt.

Regardless of the exact chemical composition of the iron-zirconium-aluminum particles, their presence in the softer zinc base matrix material is responsible forthe" markedincrease in wear resistance, particularly with the type. of wear. experienced. with dies used in drawing and forming operations. Hence the present invention provides an alloy which has proper particle distribution, as-

well as optirnum particle size, resulting in physical characteristics which satisfy all requirements for an outstand-1 ing tool alloy.

Commercially satisfactory results may be obtained in) accordance with our invention with a final zinc base alloy containing approximately 1% to 3% by weight'of hardparticles of iron-zirconium-aluminum alloy; "However;

the iron-zirconium-aluminum particles may be present instances a noticeable improvement in wear resistance results when these particles constitute as little as about 0.5% of the zinc base alloy. If the alloy contains more; than approximately 4% of these particles, the castability of the alloy is impaired and its cost becomes excessive.

Hence, a5 desirable zinc base drawing die alloy which possesses exceptional wear resistance is one consisting essentially of'about 2% to 5% aluminum, 0.5% to' 5% Accord ingly, the subject alloy is ideally suited for use as draw-' ing dies since the processing of dies formed of this 9') copper, 1% to 3% hard particles of iron-zirconiumaluminum and the balance substantially all zinc. The inclusion of approximately 0.02% to 0.3% magnesium is beneficial to reduce the corrosive tendencies of impurities such as lead, cadmium and tin. It will be understood, of course, that the zinc base alloy also may contain small amounts of silicon and other elements as incidental impurities.

Thus it can be seen that in accordance with our invention a zinc base alloy containing at least approximately 85% zinc has it wear resistance appreciably improved by the presence of the aforementioned hard ironzirconium-aluminum particles. It will be understood, however, that the term zinc base alloy, as used herein, is intended to encompass those alloys in which zinc is the major constituent and preferably constitutes at least 50% of the alloy.

More specifically, we have obtained outstanding wear characteristics in a cast alloy consisting essentially of 87% to 93% zinc, 3% to aluminum, 2% to 3.5% copper, 0.05% to 0.2% magnesium, and 1% to 3% ironzirconium-aluminum alloy in the form of dispersed hard particles. An alloy consisting of approximately 4% aluminum, 0.15% magnesium, 3.25% copper, 1.5% ironzirconium-aluminum and the balance zinc plus incidental impurities appears to possess optimum castability and wear resistance properties.

Wear resistance, of course, is a function of both the size and distribution of the hard iron-zirconium-aluminum particles. Since particle size and distribution are dependent on such factors as metal viscosity, solidification rates and methods of alloying, this invention also provides a preferred procedure for preparing the zinc base alloy. In the case of a drawing die it is desirable to produce maximum wear resistance without causing scoring of the part being drawn.

The iron-zirconium-aluminum alloy can be initially prepared by melting together the three individual constituents. Commercially pure zirconium and aluminum, such as 25 aluminum, may be conveniently used. Alternatively, of course, commercially available zirconiumaluminum alloy may be added to molten iron to form the pre-alloy. The resultant pre-alloy may contain small amounts of other metals, such as manganese, silicon, chromium, magnesium and nickel. Normally the maximum quantity of these metals would not exceed approximately 5% manganese, 2% silicon, 1% chromium, 1% magnesium, and 0.5% nickel. These percentages of the minor constitutents are not critical in most instances, however, and are listed as examples only.

Inasmuch as the iron-zirconium-aluminum pre-alloy does not readily dissolve in the zinc-rich melt, it is preferred to introduce these hard particles in the form of an intermediate alloy or hardener containing copper. When the iron-zirconium-aluminum is added to molten copper, it is transformed substantially into the molten state and is absorbed by the molten copper. During solidification of the intermediate alloy, the solubility of the iron-zirconium-aluminum is decreased and is therefore preferentially isolated as a network in the copperrich matrix. In order to form long-wearing particles of suitable size, this hardener is preferably added to the zinc in the solid state. Since it is desirable to cast the copper base intermediate alloy in shapes in which the copperrich matrix will dissolve most readily in the molten zincrich alloy, it is preferred to form castings having a high ratio of surface area to volume, such as flat plates or thin sheets. Generally the formed iron-zirconium-aluminum particles have diameters in the order of about 0.001 inch. If the particles are much smaller than this, the wear re sistance of the final zinc base alloy is not increased to the desired extent.

Upon introduction of the intermediate alloy to the zincrich melt, the copper or copper-rich matrix is dissolved, leaving the relatively insoluble network of iron-zirconiumaluminum suspended in the zinc as wear-resistant particles of appropriate size. Agitation of the zinc-rich melt causes these particles to become generally uniformly dispersed through the melt, and the particles remain so dispersed in the solidified zinc base casting.

The desired drawing die alloy composition is preferably obtained by melting substantially pure zinc and, after elevating the temperature of the molten zinc to between about 950 F. and 1075 F., dissolving therein the aluminum to be added except that which is contained in the copperiron-zirconium-aluminum intermediate alloy. This addition of aluminum retards drossing of the zinc at higher temperatures and, if a cast iron melting pot is employed, it inhibits attack of the pot by the zinc-rich melt. After further raising the temperature of the melt to approximately1100 F. to 1300 F., an appropriate amount of the copper-iron-zirconium-aluminum hardening alloy is added in the solid state, as hereinbefore indicated. The elevated temperature should be maintained until the aforementioned copper-rich matrix in this hardening alloy is entirely dissolved, the solution rate being increased by periodic agitation. After this solution is accomplished, we have found it desirable to lower the temperature of the melt to approximately 900 F. to 950 F. A suitable flux, such as ammonium chloride, may then be added to remove dross from the melt. The magnesium is there after introduced, if it is to be included in the alloy, preferably by submerging it in the bath. The final alloy may then be cast to shape in suitable molds.

Although the aluminum not included in the ir0n-zirconium-aluminum alloy can be added either before or after addition of the intermediate alloy, the above alloying sequence has been found to be most satisfactory.

-Alternatively, a, portion of this aluminum may be added prior to the introduction of the intermediate alloy and the remaining aluminum added after this alloy addition.

As hereinbefore explained, it is desirable that the ironzirconium-aluminum alloy have a density which approxi mates that of the zinc-rich melt in order to prevent floatation or segregation of the iron-zirconium-aluminum particles. The density of zinc at its melting point is 6.92 grams per cc., and the addition of about 4% aluminum decreases the density of the resultant alloy to approximately 6.9 grams per cc. Therefore, in order to obtain proper distribution of the iron-zirconium-aluminum particles, it is desirable to form these particles of an alloy having a specific gravity of about 6.5 to 7.5 grams per cc. The density of iron is 7.87 grams per cc. and the density of aluminum is 2.7 grams per cc., while the density of commercially available zirconium is about 6.5 grams per cc. Hence, we have found that an iron-zirconcium-aluminum alloy consisting essentially of 68% iron, 20% zirconium and 12% aluminum provides excellent results. Such an alloy has a calculated density of about 6.99 grams per cc., which is slightly higher than the specific gravity of the aforementioned zinc-rich melt. Based on density requirements, therefore, the iron should constitute about 55% to of the iron-zirconium-aluminum alloy. Moreover, there appears to be a tendency for the particles of this alloy to dissolve in the zinc if the iron content is above approximately We prefer to have a ratio of zirconium to aluminum in the iron-zirconium-aluminum alloy of about 1.6 to 1, but an appreciable variation in the relative amounts of these three constituents is permissible. Thus we have found that the wear resistance of a zinc base alloy may be substantially improved with an iron-zirconium-aluminum pre-alloy comprising approximately 12% to 25% zirconium, 8% to 20% aluminum and the balance iron. Such a pre-alloy produces particles of optimum size and density. In some instances, however, this pre-alloy may contain as little as 8% or as much as 30% zirconium, and the aluminum content may vary from about 5% to 25%.

When the iron-zirconium-aluminum pre-alloy is mixed with the molten copper, usually at a temperature of acre-a24- 2200 Fjto 2700 F., it'is'preferred to form-an intermediate alloy containing approximately 55 to 90% copper. If this alloy has a copper content less than 55%, it is difficult to place the copper-rich matrix'of the copper-ironzirconium-aluminum intermediate alloy in solution in the zinc-rich melt. Therefore, a copper base alloy comprisfinal alloy, although 3% to 6.5% is preferred. When such an intermediate'all'o'y is added to agzinc rich melt, it introduces into the final alloy approximately 0.35% to 2.6% iron, 0. l% to 0.8% zirconium and 0.06% to 0.5% aluminum in the form of iron-zirconium-aluminum particles and about 0.5% to 5% copper which is not combined with these particles. I

Since the hard particles'result'principallyfrom the combination of aluminum andziroonium and are formed during the preparation of the pre-alloy, the alloying procedure employed in forming the hardener is of importance in achieving optimum results. Accordingly, the iron-zirconium-aluminum pre-alloy maybe compounded by melting together the proper amounts'of iron, zirconium and aluminum,-preferably at a temperature of approxi mately 2900 F. to 3100 F. Inasmuch as zirconium is a rather readily oxidizable and nitridable element, it is desirable to use an inert gas as themelting atmosphere. We have obtained most satisfactory rnelting and high zirconium recovery using an induction furnace under an argon atmosphere It will be. noted that it is necessary to form particles of iron-zirconium-aluminum in order to obtain high wear and score resistance in accordance with the invention. Merely adding the iron, zirconium and aluminum separately to the zinc-rich melt, even if these constituents are introduced in the aforementioned preferred proportions, does not form these hard particles or provide the necessary wear resistance. It is the alloy of iron, zirconium and aluminum, rather than the individual elements, which contributes the desirable properties of wear and score resistance to the final zinc base alloy.

Wear tests were conducted to compare zinc base alloys formed in accordance with our invention with the same material devoid of iron-zirconium-aluminum particles. Samples 1% inch wide and inch high were prepared from the cast zinc base alloys to be tested, and each specimen was machined at one edge to prepare a A; inch by 1% inch rubbing surface. The specimens were next successively locked in a fixture of a wear test machine and placed in contact with a rotating smooth-surfaced wheel of low carbon steel having a face width of one inch. In creased wear resistance was measured by decreased weight loss in grams.

A wear test using this apparatus was conducted in which the specimen load was increased during a five-hour period from zero load and automatically adjusted'to produce a constant frictional load rather than a constant load normal to the wheel. This test included a ten minute run-in period in which only the weight of the specimen being tested and its holder bore against the wheel, a period of 1% hours to load the specimen to 500 pounds, a 30 minute period at 500 pounds to establish the frictional characteristics, and the balance of the five hours run with this established value of friction maintained constant. After each test any loosely adhering, deformed metal and burrs were removed from the wear test sample, and loss in weight values were used in comparing the wear resistance of the specimen.

At the end of the test period the zinc base alloy specimens formed from a zinc base alloy consisting essentially of 3.25% copper, 4% aluminum, 0.1% magnesium and the balance zinc showed an average weight loss of 0.4764

gram. On the other hand, a zinc base die alloy specimen of similar composition but containing the aforementioned preferred amounts of the iron zirconium-aluminum particles lost'an average-of only approximately 0.0436 gram. The results of this test show how greatly the presence of dispersed particles of the hard iron-zirconium-aluminum alloy increases the Wear resistance of zinc base alloys.

Although the final alloy formed has been described as particularly suitable as a drawing die material, it also may be employed to considerable advantage in other applications in which high wear resistance, goodcastability, uniformity of properties throughout a cast section, good' machinability,and anti-score properties are of importance,

'While we have set forth herein specific examples of zinc base alloys possessing high wear resistance charac teristics due to thepresence of hard particles of ironzirconiurn-aluminum, it is not intended to restrict the in ventiofi to any specific izinc base alloy. We believe that we are the'first to discover the value of adding these particles to zinc base alloys generally, and the invention is not to be restricted except as defined in the following claims." We'claim: l. A zinc base alloy characterized, by high wear re-' sista'nce comprising at least 85% zinc and approximately 0.5 to 4% iron-zirconium-aluminum particles, said particles consisting essentially of about 8% to 30% zirconium, 5% to 25% aluminum and the balance substantially all iron. 1 I

2.' A--"zi-nc*-base' alloycharacterized by high wear resistance containing at least approximately 85% zinc and about 1% to 3%"0'f hardiron-zirconium-alurninum particles dispersedfthrou'ghoutthe alloy, said particles com prisingapproximately"55%' to iron, 12% to 25% zirconium and 8% to 20% aluminum.

3. An alloy comprising approximately 2% to 5% aluminum, 0.5 to 5% copper, 0.5 to 4% hard particles of iron-zirconium-aluminum alloy, and the balance substantially all zinc, said particles comprising approximately 55% to 80% iron, 12% to 25% zirconium and 8% to 20% aluminum.

,4. A'highly wear-resistant zinc base alloy consisting essentially of about 2% to 5% aluminum, 0.5% to 5% copper, 0.02% to 0.3% magnesium, 0.5% to 4% hard particles of iron-zirconium-aluminum alloy and the balance zinc plus incidental impurities, said particles comprising approximately 55 to 80% iron, 12% to 25 'zirconium and 8% to 20% aluminum.

5. A casting alloy consisting essentially of about 3% to 5% aluminum, 2% to 3.5% copper, 0.05% to 0.2% magnesium, approximately 1% to 3% hard iron-zirconiumaluminum particles, and the balance substantially all zinc and incidental impurities, said particles comprising approximately 55 to 80% iron, 12% to 25% zirconium and 8% to 20% aluminum.

6. A zinc base alloy characterized by outstanding wear resistance and comprising approximately 2% to 5% aluminum, 0.5% to 5% copper, 0.35% to 2.6% iron, 0.1% to 0.8% zirconium, and the balance substantially all zinc plus incidental impurities, most of said iron and zirconium and 0.06% to 0.5 of said aluminum being present in the form of hard particles of iron-zirconium-aluminum dispersed throughout said zinc base alloy.

7. An alloy consisting essentially of about 3% to 5% a1uminum,'2% to 3.5% copper, 0.05% to 0.2% magnesium, 0.35% to 2.6% iron, 0.1% to 0.8% zirconium and 87 to 93% zinc, 0.06% to 0.5 of said aluminum being combined with said iron and zirconium in the form of hard particles of iron-zirconium-aluminum alloy.

8. A zinc base alloy characterized by high wear resistance comprising at least zinc, minor proportions of aluminum and copper, and approximately 0.5 to 4% hard iron-zirconium-aluminum particles generally uniformly dispersed throughout said alloy, said particles con 7 sisting essentially of about 12% to 25% zirconium, 8% to aluminum and the balance substantially all iron.

9. A method of increasing the Wear resistance of a zinc base alloy Which comprises adding to a zinc-rich melt a pre-alloy constituting 0.5% to 4% of the final alloy and consisting essentially of about 55% to 80% iron, 8% to 30% zirconium and 5% to aluminum.

10. In a method of preparing a highly Wear-resistant zinc base alloy, the step which comprises adding to a zincrich melt a pre-alloy containing iron-zirconium-aluminum Which forms in the resultant zinc base alloy, upon solidifi' cation thereof, an amount of dispersed hard particles of iron-zirconium-aluminum equal to approximately 0.5 to 4% of said zinc base alloy, said hard particles consisting essentially of about 8% to zirconium, 5% to 25% aluminum and the balance substantially all iron.

11. In a process of forming a wear-resistant zinc base alloy, the step which comprises dissolving in a zinc-rich melt a pre-alloy consisting essentially of about 5% to iron, 1.5% to 11% zirconium, 0.8% to 8% aluminum and the balance substantially all copper, said pre-alloy being added in an amount sufficient to produce an ironzirconium-aluminum content in the final alloy of approximately 0.5% to 4%.

12. A process of forming a wear-resistant zinc base casting alloy which consists of melting commercially pure zinc, dissolving therein at a temperature of approximately 950 F. to 1075 F. a quantity of aluminum equal to 2% to 5% of the final alloy and a pre-alloy consisting essentially of about to copper, 5% to 35% iron, 1.5% to 11% zirconium and 0.8% to 8% aluminum, said pre-alloy being added in an amount such that the sum of the iron, zirconium and aluminum contents thereof constitute approximately 0.5 to 4% 0f the final zinc base til alloy, and thereafter fiuxing the melt to remove objection able oxides.

13. A process of forming a wear-resistant zinc base casting alloy which consists of melting commercially pure zinc, dissolving therein at a temperature of approximately 950 F. to 1075 F. a quantity of aluminum equal to about 2% to 5% of the final alloy, raising the temperature of the resultant zinc-rich melt to between approximately 1100 and 1300 F., thereafter adding to said melt a pre-alloy consisting of copper, iron, zirconium and aluminum, the composition of said pre-alloy being such that the final alloy contains 0.5% to 5% copper, 0.35% to 2.6% iron, 0.1% to 0.8% zirconium and 2% to 5% aluminum,- reducing the temperature of the zinc-rich melt to about 900 F. to 950 F., fiuxing said melt to remove objectionable oxides, and subsequently dissolving in the melt an amount of magnesium equal to 0.02% to 0.3% of the final alloy.

References (Iitedl in the file of this patent UNITED STATES PATENTS 1,151,160 Brown Aug. 24, 1915 2,048,288 Pierce et al. July 21, 1936 2,317,179 Daesen Apr. 20, 1943 2,372,546 Bunn Mar. 27, 1945 2,504,935 Morris Apr. 18, 1950 2,641,540 Mohling. et al. June 9, 1953 2,747,989 Kirkby et al. May 29, 1956 2,795,501 Kelly June 11, 1957 FOREIGN PATENTS 138,348 Great Britain Apr. 27, 1921 1,036,896 France Apr. 29, 1953 

1. A ZINC BASE ALLOY CHARACTERIZED BY HIGH WEAR RESISTANCE COMPRISIANG AT LEAST 85% ZINC AND APPROXIMATELY 0.5% TO 4% IRON-ZIRCONIUM-ALUMINUM PARTICLES, SAID PARTICLES CONSISTING ESSENTIALLY OF ABOUT 8* TO 30% ZIRCONIUM 5% TO 25% ALUMINUM AND THE BALANCE SUBSTANIALLY ALL IRON. 